Thermodynamic assessment of the Ti–B system

A consistent thermodynamic data set for the Ti–B system is obtained by means of CALPHAD technology. The sublattice model is used to describe the solid solution phases: (Ti%)₁(B, Va%)_0.5 and (Ti%)₁(B, Va%)₃ for the terminal solution (Ti) and (βTi), and Ti₁(B%, Ti)₁ and (B, Ti%)₁(B%, Ti)₂ for the compound solution TiB and TiB₂, respectively. The intermetallic compound Ti₃B₄ is treated as a stoichiometric compound. The liquid solution phase is assumed to be a substitutional solution with Redlich–Kister formula for the expression of its excess Gibbs energy. The complete T–x phase diagram for the Ti–B binary system is given. The calculation results agree well with experiments.     

The ternary system Al–Ni–Ti Part II: thermodynamic assessment and experimental investigation of polythermal phase equilibria

The Al–Ni–Ti phase diagram has been thermodynamically assessed and a consistent set of thermodynamic functions has been developed. The thermodynamic modeling is based on an experimental investigation of the phase equilibria in the composition range of 0.1x_Al0.7. Alloys were prepared by argon-arc or vacuum-electron beam melting of elemental powder blends. X-ray powder diffraction, metallography, SEM and EMPA-techniques were employed to analyze the samples in the as-cast state as well as after annealing at 800, 900 and 1000°C. The existence of the four ternary compounds, τ₁ to τ₄, has been confirmed, although homogeneity regions differ significantly from reports in the literature. The homogeneous phase, previously claimed at “Al₂₃Ni₂₆Ti₅₁”, is shown by high resolution microprobe and X-ray diffraction measurements to be an extremely fine-grained eutectic structure. The congruent melting behavior of τ₄=AlNi₂Ti is confirmed, but, in contrast to earlier reports, primary crystallization and congruent melting have been observed for τ₁=Al₁₃Ni₂Ti₅ and τ₃=Al₃NiTi₂. In contrast to earlier assessments, τ₁,τ₂ and τ₃ are experimentally found to be stable at 800, 900 and 1000°C. The thermodynamic modeling of the ternary phases τ₂ and τ₃ is done with simplified sublattice models, considering their crystal structure and homogeneity ranges. The sublattice model for τ₄ is taken from an earlier asessment of the nickel-rich ternary phase equilibria. The present assessment covers the entire composition range. An application to the solidification behavior of ternary alloys is also exemplified.     

Computer-aided thermodynamic study of solid Co---Pd alloys by Knudsen cell mass spectrometry, and calculation of the phase diagram

F.c.c. solid Co---Pd alloys have been investigated thermodynamically by means of computer-aided Knudsen cell mass spectrometry. Thermodynamic evaluation has been performed by applying the “digital intensity ratio” method. The thermodynamic excess properties can be described algebraically by means of thermodynamically adapted power series with two adjustable parameters, i.e. C₁^G (−20 810 + 9.608T) J mol⁻¹) and C₂^G (−30 720 + 6.78T) J mol⁻¹). At 1470 K, f.c.c. solid Co---Pd alloys are characterized by negative molar excess Gibbs energies G^E, exothermic molar heats of mixing (H^E) and small negative molar excess entropies S^E. At 1470 K, the minimum G^E value is −4600 J mol⁻¹ (61.9 at.% Pd), the minimum H^E value is −9400 J mol⁻¹ (59.5 at.% Pd) and the minimum S^E value is −3.3 J mol⁻¹ K⁻¹ (55.9 at.% Pd). The thermodynamic activities of Co show small positive deviations from the ideal case for the Co-rich alloys (x_Pd < 0.34), and negative deviations from Raoults' law for alloys with higher Pd contents. The Pd activities a_Pd show negative deviations from the ideal case for all compositions. The phase diagram has been computed by means of a generally applicable procedure for the calculation of the equilibrium compositions of coexisting phases. This was achieved using the results of this work, thermodynamic data from earlier mass spectrometric studies on the liquid phase, and literature data for the heat capacities and enthalpies of Co and Pd.     

Thermodynamic assessments of the Cu–Th and Mo–Th systems

The thermodynamic assessments of the Cu–Th and Mo–Th binary systems were carried out by using Calculation of Phase Diagrams (CALPHAD) method on the basis of the experimental data including the thermodynamic properties and phase equilibria. The Gibbs free energies of the liquid, bcc, and fcc phases are described by the subregular solution model with the Redlich–Kister equation and those of the four intermetallic compounds Cu₆Th, Cu_3.6Th, Cu₂Th and CuTh₂ in the Cu–Th binary system were described by the sublattice model. A set of self-consistent thermodynamic parameters are obtained, and the calculated phase diagrams and thermodynamic properties are presented and compared with the experimental data from literatures. The calculated thermodynamic properties as well as phase diagrams are in good agreement with the experimental data.     

Thermodynamic assessment of the Nd–Zn binary system

On the basis of available experimental information, the Nd–Zn binary system has been thermodynamically optimized using the CALPHAD method. The solution phases, liquid, bcc and dhcp, were treated as substitutional solutions, while the intermediate compounds, NdZn, NdZn₂, NdZn₃, Nd₃Zn₁₁, Nd₁₃Zn₅₈, Nd₃Zn₂₂, Nd₂Zn₁₇ and NdZn₁₁, were described as stoichiometric phases. A set of self-consistent parameters formulating the Gibbs energies of various phases in this binary system was obtained. Most of experimental data on thermochemistry and phase diagram reported in the literatures were satisfactorily reproduced.     

The ternary system Al–Ni–Ti Part I: Isothermal section at 900°C; Experimental investigation and thermodynamic calculation

Phase relations in the ternary system Al–Ni–Ti have been experimentally established for the isothermal section at 900°C for concentrations 0.1x_Al0.7. The investigation is based on X-ray powder diffraction, metallography, SEM and EMPA-techniques on about 40 ternary alloys, prepared by argon-arc or vacuum-electron beam melting of proper elemental powder blends. The existence of four ternary compounds, τ₁ to τ₄, is confirmed, however, in contrast to earlier investigations at significantly different compositions and with different shape of the homogeneity regions. This is particularly true for the phase regions of τ₃-Al₃NiTi₂ with the MgZn₂-type structure ranging from Al₃₀Ni₂₈Ti₄₂ (composition lowest in Al) to Al₅₀Ni₁₆Ti₃₄ (composition richest in Al) and for τ₂-Al₂NiTi. The complex atom site substitution mechanism in τ₃ changing from Ti/Al exchange at Al-poor compositions towards Ni/Al replacement for the Al-rich part was monitored in detail by quantitative X-ray powder diffraction techniques (Rietveld analyses). In contrast to earlier reports, claiming a two-phase region Ni{Al_xTi_1-x}₂+τ₃, we observed two closely adjoining three-phase equilibria: ₂-AlTi₃+Ni{Al_xTi_1-x}₂+ τ₄-AlNi₂Ti and ₂-AlTi₃+τ₃-Al₂NiTi₂+τ₄-AlNi₂Ti. The earlier reported “homogeneous phase at Al₂₃Ni₂₆Ti₅₁′” was shown by high resolution microprobe and X-ray diffraction measurements to be an extremely fine-grained eutectic. The experimental results are in fine agreement with the thermodynamic calculation.     

TIG熔敷Ti-Si-C系统在Ti-5Al-2.5Sn表面形成陶瓷涂层的化学反应分析

采用TIG热源在钛合金表面堆焊Ti-SiC和Ti-SiC-C两种体系的粉末,形成表面陶瓷涂层.利用SEM和XRD等分析手段对两种配方陶瓷涂层的微观组织和物相进行了分析,用热力学方法计算了两种系统中各种可能发生的化学反应的Gibbs自由能变化.结果表明,Ti-SiC系统熔敷层的微观组织主要由树枝状的TiC、针棒状和菊花状的Ti₅Si₃相组成,其反应机理为:8Ti+3SiC→3TiC+Ti₅Si₃.Ti-SiC-C系统熔敷层的微观组织除了树枝状的TiC相之外,还有TiSi₂和Ti₃SiC₂,其反应机理为:6Ti+3SiC+C→Ti₃SiC₂+TiSi₂+2TiC.通过对两种系统的微观组织及化学反应分析可得出,在Ti-SiC系统中适当的添加石墨,可生成具有自润滑性能的Ti₃SiC₂相,避免Ti₅Si₃脆性相的生成.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

Oxygen release behaviour of Ce(1−x)ZrxO2 powders and appearance of Ce(8−4y)Zr4yO(14−δ) solid solution in the ZrO2–CeO2–CeO1.5 system

To clarify the existence of metastable phases in the ZrO₂–CeO₂–CeO_1.5 system, evolved-oxygen gas analyses, (EGA), by heating a single phase of t′ and t″ (Ce_(1−x)Zr_xO₂) with various compositions, x, in a reducing gas and successive oxidation were carried out repeatedly. The oxygen release behaviour of the t′ and t″ phases was very complicated. The single κ phases, (Ce_(1−x)Zr_xO₂) with the composition, x=0.5 and 0.6, which were obtained by oxidizing the resulting pyrochlore as a precursor in O₂ gas at 873 K, exhibited a sharp oxygen release at the lowest temperature; the composition range of κ phase may be x=0.450.65. A new tetragonal phase t*, (Ce_(1−x)Zr_xO₂), which was attained by cyclic redox process together with annealing in O₂ gas at 1323 or 1423 K, exhibited a sharp oxygen release at the highest temperature; the composition range of t* phase may be as wide as x=0.200.65. A metastable solid solution expressed by a chemical formula of Ce_(8−4y)Zr_4yO_(14−δ) (y=01) possessing a CaF₂-related structure appeared on deoxidation of the t* phase. A ternary phase diagram containing the t* and Ce_(8−4y)Zr_4yO_(14−δ) solid solution was proposed.     

First-principles investigations of isotope effects in thermodynamic properties of TiX2 (X = H, D, and T) system

As hydrogen, deuterium and tritium storage materials, a series of investigations of mechanical and thermal properties of titanium hydrides, deuterides and tritides have been performed, however, very limited theoretical studies of thermodynamic properties for them can be found. Based on density-functional theory (DFT) and density-functional perturbation theory (DFPT) we have discussed systematically the hydrogen isotope effects on the thermodynamic properties of TiX₂ (X = H, D, and T) system. Our calculations indicate that for evaluating accurately their physical properties at absolute zero temperature, such as the equilibrium lattice constants, bulk modulus, and heat of formation, the zero-point energy correction must be taken into account. By performing the phonon calculation within quasiharmonic approximation (QHA), we obtain their vibrational free energies, vibrational entropies, and temperature dependence of specific heat, thermal expansion, and bulk modulus. Those results demonstrate that comparing with TiH₂, TiT₂ and TiD₂ are more stable and the zero-point effects play an important role in their thermal expansion. The increase in the force constant between Ti and H causes the higher value of specific heat of TiH₂ during the phase transition from FCC to FCT. In addition, comparing with available experimental values, we can conclude that QHA is feasible for describing the thermal properties of TiX₂.     

Observation of hydrogen absorption/desorption reaction processes in Li–Mg–N–H system by in-situ X-ray diffractmetry

The in-situ XRD measurements on dehydrogenation/rehydrogenation of the Li–Mg–N–H system were performed in this work. The ballmilled mixture of 8LiH and 3Mg(NH₂)₂ as a hydrogenated phase gradually changed into Li₂NH as a dehydrogenated phase during heat-treatment at 200 °C in vacuum for 50 h. Neither Mg-related phases nor other intermediate phases were recognized in the dehydrogenated phase. With respect to the hydrogenation process, the dehydrogenated state gradually returned to the mixed phase of the LiH and Mg(NH₂)₂ without appearance of any intermediate phases during heat treatment at 200 °C under 5 MPa H₂ for 37 h and during slow cooling down to room temperature through 24 h. In the hydrogenation process at 200 °C under 1 MPa H₂, however, the growing up of the LiNH₂ and LiH phase was observed in the XRD profiles before the 3Mg(NH₂)₂ and 8LiH phases were formed as the final hydrogenated state. This indicates that the LiNH₂ and LiH phase essentially appears as an intermediate state in the Li–Mg–N–H system composed of 3Mg(NH₂)₂ and 8LiH.     

Phase Stability in Mechanically Alloyed Mg–Ni System Studied by Experiments and Thermodynamic Calculations

In this study, microstructural evolution of Mg–Ni alloy during mechanical alloying(MA) was investigated.Also, a thermodynamic approach was utilized to predict the most stable phases formed in Mg–Ni alloy after MA. The phase composition and microstructural properties of Mg–Ni alloy were assessed by X-ray diffractometry, high-resolution field emission scanning electron microscopy and high-resolution transmission electron microscopy. The results showed that ball milling of magnesium and nickel powder mixture for 70 h yields nanostructural Mg2Ni compound with an average grain size of ~20 nm. Thermodynamic calculations revealed that in the composition ranges of 0.0 \ XMg\ 0.03(at.%)and 0.97 \ XMg\ 1, there is no driving force for amorphous phase formation. In the composition range of 0.07 \ XMg\ 0.93, the change of Gibbs free energy for amorphous phase formation was more negative than solid solution.While for XMg= 0.66(nominal composition of Mg2Ni intermetallic phase), the change of Gibbs free energy for intermetallic phase was found to be more negative than both amorphous and solid solution phases indicating that Mg2Ni intermetallic compound is the most stable phase, in agreement with the experimental observations.     

Thermal stability and hyperfine interactions of mechanically alloyed Fe–Ge phases

Mechanical alloying method was applied to prepare the Fe₇₅Ge₂₅, Fe₆₂Ge₃₈ and Fe_33.3Ge_66.7 alloys. X-ray diffraction, differential scanning calorimetry and Mössbauer spectroscopy were used as complementary methods to obtain structural data and hyperfine interaction parameters for the as-milled as well as the heated samples. After mechanical alloying process the disordered -Fe(Ge) solid solution was formed in the case of Fe₇₅Ge₂₅ composition and it was characterized by the broad hyperfine magnetic field distribution with the average field of about 25 T. Heat treatment up to 873 K resulted in the formation of the mixture of three ordered phases and -Fe(Ge) solid solution. The ordered phases were: metastable D0₃ phase with two hyperfine magnetic fields of 32.8 and 20.2 T and two equilibrium phases—hexagonal and cubic ′ with fields of about 24.6 and 23.6 T, respectively. After heating up to 973 K this mixture transformed into the mixture of and ′ phases. In the case of Fe₆₂Ge₃₈ composition the hexagonal β-Fe₃Ge₂ phase was obtained during mechanical alloying process. This phase was stable after heat treatment up to 973 K. The as-milled and heated samples were characterized by similar Mössbauer spectra, which were a superposition of the sextets with various hyperfine magnetic fields what reflected different configurations of germanium atoms around ⁵⁷Fe atoms. In the case of Fe_33.3Ge_66.7 composition the ordered tetragonal FeGe₂ phase was obtained and it was stable during heat treatment up to 973 K. Mössbauer measurements revealed the single paramagnetic line with the isomer shift of 0.30(1) mm/s characteristic for the FeGe₂ intermetallic phase.     

Dissolution theory of gold in alkaline thiourea solution(

The oxidants of gold were investigated in an alkaline thiourea solution containing Na₂CO₃, in which Na₂S₂O₈ is a proper oxidant for dissolving gold because of in such homogeneous sulfur system coexisting complex agent, oxidant and stabilizing agent. The thermodynamic analyses were conducted on the dissolving of gold in the alkaline thiourea solution containing Na₂SO₃ by the oxidants oxygen or Na₂S₂O₈. The results show that the possibility of gold dissolution reduces with increasing pH value, while oxygen acts as oxidant; and when Na₂S₂O₈ acts as the oxidant of gold in the alkaline thiourea solution of pH 12.5, decomposition potential of thiourea decreases from the standard value 0.42 V to -0.32 V, also the dissolution trend of gold enhances with shifting the mix potential of the solution to the positive direction.     

Magnetic phase transition in Ti-doped ErCo2 alloys

The homogeneity range of U₂Co_17−xSi_x system with the hexagonal Th₂Ni₁₇-type crystal structure extends from x = 1 to 3.4. The variation of the magnetic properties within the homogeneity range was studied on single crystals. All the compounds are ferromagnetic, M_s and T_C decrease monotonously with increasing Si content. The strongly modified magnetic anisotropy of U₂Co_17−xSi_x, as compared to isostructural Lu₂Co_17−xSi_x with the non-magnetic Lu, points to a magnetic state of U up to x = 3.0. The U contribution to K₁ decreases with increasing Si content and vanishes at x = 3.4 that can be treated as a transition from magnetic to non-magnetic state of U. Spin reorientation was observed with varying temperature in compounds with x ≤ 3 due to a competition of the U and Co sublattices anisotropies which occurs as two second-order phase transitions of the “plane–cone” and the “cone–axis” type.